Synthesis and Structure of 12-Member Ring Crown-Shaped Oxovanadium Borophosphate Polyanions:  [H₃NC₂H₄NH₂C₂H₄NH₂C₂H₄NH₃]₄H[M(VO)₁₂{O₃POB(O)₂OPO₃}₆]·nH₂O (M = NH₄⁺, K⁺)

Abstract

Using multiethylenemultiamine to direct the crystallization of inorganic frameworks through multipoint hydrogen bonds, two new oxovanadium borophosphates, denoted VBP-J1 and VBP-J2, have been synthesized by hydrothermal methods as well as under reflux conditions. Powder X-ray diffraction patterns indicate that VBP-J1 and VBP-J2 are structural analogues. Structure determinations show that both VBP-J1, [H3NC2H4NH2C2H4NH2C2H4NH3]4H[NH4(VO)12{O3POB(O)2OPO3}6]·14H2O and VBP-J2, [H3NC2H4NH2C2H4NH2C2H4NH3]4H[K(VO)12{O3POB(O)2OPO3}6]·16H2O crystallize in the orthorhombic space group Pbca with crystal data: a = 21.454(11) Å, b = 16.315(6) Å, c = 29.651(12) Å, α = β = γ = 90°, V = 10378(8) Å3, Z = 4 for VBP-J1 and a = 21.537(2) Å, b = 16.2667(13) Å, c = 29.717(4) Å, α = β = γ = 90°, V = 10410.8(18) Å3, Z = 4 for VBP-J2. VBP-J1 and VBP-J2 are constructed by edge-sharing {V2O10} binuclear unit and {BP2O10} trimer to form interesting 12-member ring crown-shaped clusters with NH4 + and K+ cations encapsulated in the clusters. The ring diameters are 5.873 × 5.412 × 5.561 Å for VBP-J1 and 5.758 × 5.421 × 5.236 Å for VBP-J2. An extended network of multiple hydrogen bonds among anions, cations, and water molecules links the structure in three dimensions.

[Co(en)3][B2P3O11(OH)2]: A Novel Borophosphate Templated by a Transition-Metal Complex

“…The interest in borophosphates has been steadily growing after the discovery of the first borophosphate with an open-framework structure, the ethylenediamine-templated Co II B 2 P 3 O 12 (OH)·enH 2 − In addition to these, a few organically templated borophosphates, all based on vanadium and mostly low-dimensional, are known …”

Offene Gerüststrukturen von Übergangsmetallen

“…In vielen Übergangsmetalloborophosphaten sind diese Einheiten durch Metalloktaeder verbunden 140. Die Struktur von [H 3 NC 2 H 4 NH 2 C 2 H 4 NH 2 C 2 H 4 NH 3 ] 4 H[M(VO) 12 (BP 2 O 10 ) 6 ]⋅ n H 2 O (M=NH 4 + , K + ) wird von Zwölferringen aus [(VO) 12 (BP 2 O 10 ) 6 ] 18− ‐Clustern gebildet 140a. Dieser Cluster entsteht durch die Verknüpfung von sechs BP 2 O 10 ‐ und sechs V 2 O 10 ‐Einheiten, wobei die NH 4 + ‐ oder K + ‐Ionen im Innern der Ringe eingeschlossen sind.…”

“…Eine Baueinheit der Zusammensetzung (VO) 2 BP 2 O 10 , die durch die Verknüpfung von BP 2 O 10 ‐ und V 2 O 8 ‐Einheiten über gemeinsame Sauerstoffatome entsteht, wurde in [C 4 N 2 H 12 ] 6 [(VO) 2 BP 2 O 10 ] 4 ⋅ n H 2 O ( n =2,6,14) nachgewiesen,140b in dem sie cyclisch zum Tetramer [(VO) 2 BP 2 O 10 ] 4 12− verbunden ist. In [H 3 NCH 2 CH 2 NH 3 ][(VO) 5 (H 2 O)(BP 2 O 10 ) 2 ]⋅1.5 H 2 O sind die [BP 2 O 10 ] 7− ‐Ionen durch VO 6 ‐Oktaeder zu einer zweidimensionalen Schicht verknüpft140e und anders als in den Clusterverbindungen140a, b auch zur dreidimensionalen Struktur, deren eindimensionale Kanäle von den Ethylendiaminmolekülen besetzt werden.…”

Layered V–B–O polyoxometalate nets linked by diethylenetriamine complexes with dangling amine groups

“…In most of the vanadoborates, the clusters are closed as cage-like clusters, such as V 12 B 16 , 19 V 12 B 17 , V 12 B 18 , 20 V 10 B 28 , 21 and V 6 B 20 , 22 as summarized in our previous paper, 20,23 except for the rare ring-like V 12 B 32 cluster. 24 Compared to the cagelike clusters in vanadoborates, vanadium borophosphates are more likely to form ring-like clusters [25][26][27][28] although the sheetlike 29,30 and cage-like [31][32][33] clusters in vanadium borophosphates were also reported. They can form open 8-rings and 12-rings with various B : P : V ratios under different experimental conditions.…”